Sulphonic derivatives



Patented Aug. 12, 1941 SULPHONIC DERIVATIVES Morris Katzman, Chicago, 111., assignor to The Emulsol- Corporation, Chicago, Ill., a corporation of Illinois N Drawing. Application July 7, 1939,

Serial No. 283,141

20 Claims.

This invention relates to new chemical compounds in the form of sulphonic derivatives which are characterized by possessing interface modifying properties rendering the same highly useful for the purposes for which such agents are employed in the various arts. The invention-also relates to novel intermediate compounds having utility for divers purposes.

The substances of the invention are, in general, higher molecular weight esters or ethers of aliphatic sulpho-poly-carboxylic acid amides of alcoholor alkylol-primary onsecondary amines. More particularly, and as exemplified by the preferred embodiments of the invention, they are higher molecular weight fatty acid esters of lower molecular weight aliphatic sulpho-dicarboxylic acid amides of monohydroxy alkylolamines.

At least most of the novel sulphonlc compounds fall within the scope of the general formula wherein R is .an organic radical containing at least four carbon atoms, alk stands for hydrocarbon, for example, alkylene, or arylene such as ethylene or phenylene, Y is hydrogen, alkyl, cycloalkyl, alkoxyl, aralkyl, aryl, or alkylol, -COZ is the carboxylic acyl radical'of an aliphatic sulpho-poly-carboxylic acid containing preferably less than eight carbon atoms, and m'is a whole number, preferably from oneto four.

A more limited aspect of the compounds of the invention may be represented by the general formula atoms. Alk, likewise, may contain substituent' groups such as amino, hydroxy, halogen, sulphate, sulphonic, phosphate, carboxyl, nitrile, and the like, and the sequence of carbon atoms therein may be interrupted by O, S,"C =O, NH, NR, where R is alkyl, and the like.

In order that the nature of the invention may become apparent, there are listed hereinbelow representative compounds which fall within the scope of the invention:

H S OaNa HF-O-CH:

O JJHr-CHa-CHrCH-JJHr-C 00K C-OCH:-CH:NH-C OCH:CHC O O K HaC-CH:

H2O CH-C-O-CHr-CHa-NH-C O-GHz-CH-COONB Inc-0H, O1Na H OiNa (17) CiiHn-CrO-CHs-CHa-OHrCHrNE-COCH|-CH-S0|K (18) o lnn-o-o-clul-nn-oo onrcn-ooon.NE(o,Hal

oar-Acme;

" 22) CuHa-Cf-C-eOnHr-IF-CO-CIIr-CIi-Q00K 1 (so c..Huo-c=m-Nn-oo-cm-cn-cnk-ooon I l r canon (an olu rc-- o-o.m -oo-on,-,cn-coon CnHn-C-O-CzHe-O-CzHa-NH-C-CHrCHrCH-CHr-OOONI O Na (2 B0gNa (m omEg-o-cen-un-c-cn-cm-coon -mary or secondary SOiNa I SOaNa onna-c-o-clnl-xn-w n-onl-o-o-onrcn-cnlon- I I H 8 OiNa as) o"Ha-c-o-oln -nn-c-en-cnro-o-cnl-cnlon (an sou:

While the above examples represent single substances, it will be understood that in practice it is, in general, more advantageous to em loy mixtures of any two or more thereof with 0 without diluents.

In general, the compounds may he prepared by initially reacting an alcoholor alkylol-prian aliphatic polycarboxyllc acid, such as monoethyl ester or maleic acid, under conditions such as to insure a substantial yield of amide. It has been found-that with such reactants and the utilization of low temperatures, of the order of about 0 degrees C. to about 10 degrees C., excellent yields of amide are obtained. The resulting amide is thenreacted with a higher molecular monium bisulphite.

weight organic acid or halide or otherderivative thereof to produce the ester and with a bisulphite, for example,

group into the molecule. 1i desired,'prior to the treatment with may be reacted with hypochlorous acid or hypobromous acid, hydrogen halide, halogen or the like to introduce halogenat the doubiebond oi the maleic acid radical or the like, and the resulting compoundis then treated with a sulphite 505 such assodium, potassium, ammonium or lithium sulphite.

' Another method which may be employed effectively to produce vention comprises the compounds of the inreacting an alcoholor alk'ylol-primary or secondary amine, such as monoethanolamine, with a poly-carboxylic acid anhydride, such as maleic anhydrlde, to produce the amide, for example, the 'maleic acid amide oi monoethanolarnine. The resulting compound is then reacted with a bisulphite, particularly an alkali bisulphite, to introduce a sulphonic group and then with an acyl halide, such as lauroyi chloride, to esteriiy the free hydroxyl group or groups or the alcohol amine. The following examples are illustrative oi methods which .have been found suitable rmpreparing various of the compounds which are-dis-' closed herein. It will be appreciated that other methods may be utilized and that the proportions ofreacting ingredients, times or reaction,- and temperaturesmay be variedorder or steps, and that supplementary processes of purification and, th like may be resorted, to wherever round desire is or co venient. These are other variations and modifications will be evident to amine, including correspond- V ing polyamines, for'example, monoethanolamine, with a lower molecular weight alcohol ester oi! sodium, potassium, or am- 7 to introduce a sulphonic,

the bisulphite, the productthose skilled in the art in the light of the guiding principles which are disclosed herein.

Example A 6.1 grams of monoethanolamine were dissolved 5 in 25 cc. of dry dioxane and this solution was added slowly, with constant stirring, to grams of maleic anhydride. The temperature rose to 70 degrees C. over a period of about 10 minutes.

The resulting clear solution was then cooled to 10 '40 degrees C. and 20 cc. of lauroyl'chloride were added dropwise over a period of about 5 minutes. The temperature rose to approximately 60 degrees, C. and the mixture became homogeneous.

It was then heated, to 80 degrees C. and maintained atsuch temperature for about 5 minutes. To the resulting reaction product, 50 cc. of water and 25 grams of potassium bisulphite were added and the mixture was heated, with stirring,

for about 10 minutes at 60 degrees C. The prodnot became a jelly-like liquid having good foaming and wetting properties.

In order to purify the product, 20 grams of the reaction mass were extracted with 120 cc. of boiling isopropyl alcohol, the solution wasthen cooled down and filtered and the residue, which was a white solid and possessed good water solubility and foaming properties, comprised essentially a product having the following probable formula:

0 03K Example B 10.5 grams of diethanolamine were dissolved in 15 cc. of pyridine and there were added thereto 10 grams of maleic anhydride dissolved in'15 cc. of pyridine. The temperature rose from 25 degrees C. to approximately 40 degrees C. in a period of about 10 minutes.

degrees C. The reaction product, which comprised a solution having foaming and wetting 5 properties, contained a substantial proportion of a compound having the following probable formula:

13.7 grams of phenyl ethanolamine and 11 grams of maleic anhydride were mixed together at room temperature, the temperature spontao5 neously rising to approximately '10 degrees C. The reaction mass was then'heated to 100 degrees C. and maintained at that for about 5 minutes. While still at approximately 100 degrees C., 20 cc. of ,lauroyl chloride were 7.0

- usual organic solvents.

added dropwise thereto, with stirring, over a pe riod of about 10 minutes, the temperature during the;-;reaction, being,-,maintained at about degrees C. to degrees C.

- 10 grams ofthe resulting liquid reaction mixthereto, with stirring.

temperature I ture, 10 grams of sodium bisulphite and 25 cc. of water were heated, with stirring, to 60 degrees C. and maintained at that temperature for between 15 minutes and 20 minutes. The resulting reaction product, which had good foaming and wetting properties, contained a substantial proportion of a compound having the following probable formula:

' -CHzCH-COONa O OaNB If desired, the reaction mass may be evaporated down and the desired product obtained in purlfied form by extraction of extraneous matteror unreacted materials with organic solvents.

Example D 1) 10.4 grams of hydroxyethyl ethylene diamine were dissolved in 50 cc. of water and 19.6 grams of maleic anhydride were slowly added Simultaneously with the addition of the maleic anhydride, a solution comprising 14 grams of potassium hydroxide dissolved in 50 cc. of water was added dropwise, with constant stirring, over a period of about 20 minutes. The resulting solution, which was just faintly alkaline to phenolphthalein, was evaporated to dryness in an oven at a temperature of about 150 degrees C. over a period of about 2 hours. The

dried product was then cooled and ground to a powder.

('2) 17 grams of the product produced in part (1) hereof andv 10 cc. of lauroyl chloride .were mixed together andheated on the boiling water bath for 30 minutes, a vacuum being employed to The mass was then 46 draw off the hydrochloric acid as 1t,,was formed cooled to 20 degrees C. and, over a period of 10 in the reaction. The resulting reaction mass was then washed twice, in each instance cc. of petroleum ether being employed to extract the fatty matter. The residue, from which the adhering petroleum ether'was removed by warming, was then dried and powdered. I

(3) 10 grams of the dried powder produced in part (2) hereof, 10 grams of potassium meta bisulphite, and 20 cc. of water were mixed together and heated at 60 degrees 0., with constant stirring, for about 10 minutes. The resulting'solution was then cooled to room temperature and 5 cc. of a 30% aqueous solution of potassium hydroxide were added thereto to neutralize the solution to litmus. The resulting so- 5 lution possessed good foaming and wetting properties andv contained a substantial proportion not a compound having the following probable formula:

desired, by evaporation of the solution to dryness and the extraction of extraneous matter by the Example E (1) 17.5 grams of mono-ethyl ester of maleic acid and 12.3 grams of monoethanolamine were mixed together, the temperature spontaneously rising to 65 degrees C. The resulting product .was then heated. at 190 degrees C, for 20 to 30 minutes, approximately two equivalents of ethyl alcohol being volatilized. The reaction mass was cooled to 60 degreesC. and 40 grams of lauroyl chloride were added dropwise, with stirring, over a period of about 15 minutes, the mass then being allowed to stand for one hour at 60 degrees C.-70 degrees C.

(2) grams of the reaction product produced inpart 1) hereof, 10 grams of sodium bisulphite, and 20 cc. of water were mixed together'and heated for several hours, with stirring, at 70 degrees 0,-80 degrees C. The final reaction product, which was soluble and possessed foaming properties, contained a substantial proportion of a compound having the following probable formula:

In certain instances, illustration, in Example as indicated, by way of 31, a free carboxyl group may be present in the compounds. Such compounds may be further reacted to esterify or amidify the free carboxyl group to convertthe same into the groups CON'H2, -CONHR, and

3 COOR where R is preferably lower molecular weight alkyl or cyclo-alkyl such as ethyl, butyl, 1 cyclohexyl and the like, which may contain sub-. 1 stituent groups such as halogen, hydroxy, amino, cyanogen and the like. linkage, that is, the COOR group, the radical R may be that of a polyhydric alcohol or poly- In the case of the ester hydroxy substance such asglycerol, glycols and glycerols, and-the like. Such derivatives have particularly desirable properties in the industrial and technical arts. The usual amidifica'tion and esterification procedures can readily be adapted by the skilled chemist to the preparation of such derivatives.

Instead of carrying out the reactions as described hereinabove, various of the compounds of this invention may be produced by reacting an amino alkyl ester with a sulpho-poly-car- ,boxylic acid or ester of a sulphzypoly-carboxylic acyl halide in accordance, for example, with the following reaction:

lpolyglycols such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, poly- As Examples 6, 15 and ,16 show, the compounds may also comprise higher molecular weight ether derivatives. The higher molecular weight ethers may be prepared, for example, by reacting a com-- pound containing a reactive halogen,'for example,

with an alkali metal alcoholate such as sodium laurylate (C12H25ONa) in accordance with general methods known in the art. In general, the higher molecular weight esters are more satisfactory for most purposes.

The organic radical represented by R in the general formulae may, as stated, be derived from various sources. Among such sources may be mentioned straight chain and branched chain carboxylic, aliphatic, and fatty acids, saturated and unsaturated, such as butyric acid, capyrylic acid, caproic acid, capric acid, sebacic acid, be-- henic acid, arachidic acid, cerotic acid, erucic acid, melissicacid, stearic acid, oleic acid, recinoleic acid,linoleic acid,linolenic acid, lauric acid,myristic acid, palmitic acid, mixtures of any two or more of the above mentioned acids or other acids, mixed higher fatty acids derived from animal or vegetable sources, for example, lard, coconut oil, rapeseed oil, sesame oil,.pa1m kernel oil, palm oil, olive oil, corn oil, cottonseed oil, sardine oil, tallow, soya bean oil, peanut oil, castor oil, seal oils, whale oil, shark oil, partially or completely hydrogenated animal and vegetable oils such as those mentioned; oxidized and/or polymerized higher fatty acids or higher fatty acids derived from oxidized and/or polymerized triglyceride oils; hydroxy and alpha-hydroxy higher aliphatic and fatty acids such as i-hydroxy stearic acid, dihydroxystearic acid, alpha-hydroxy stearic acid, alpha-hydroxy palmitic acid, alpha-hydroxy lauric acid, alpha-hydroxy coconut oil mixed fatty acids, and the like; fatty acids derived from various waxes such as beeswax, spermaceti, montan wax, and carnauba wax and carboxylic acids derived, by oxidation and other methods, from petroleum; cycloaliphatic and hydroaromatic acids such as hexahydrobenzoic acid, resinic acids, naphthenic acid and abietic acid; aromatic acids such as phthalic acid, benzoic acid, naphthoic acid, pyridine carboxylic acids; hydroxy aromatic acids such as salicyclic acid, hydroxy benzoic and like; and substitution and addition derivatives, particularly halogen substitution and addition derivatives of the aforementioned carboxylic substances. It will be understood that mixtures of i any two or more of said acids may be employed It will be understood, particularly in the light of the examples hereinabove, that the novel compounds of the present invention may contain one or more imino or like linkages. Thus, for

if desired;

In those cases where higher molecular weight organic radical is derived from alcoholates of alcohols corresponding to the higher molecular hereinabove.

example, in place of employing monoethanolamine or monopropanolamine or the like as a starting material, compounds may be utilized having a pluralityof imino' groups such as the following, by way of illustration:

The aliphatic sulpho-poly-carboxylic acid radi- I cals present in the compounds of my invention may be selected from a relatively large class ineluding, for example, those of sulpho-succinic" in general, the best results are obtained when the naphthoic acids, and the ethers are prepared, the

weight acids referred to sulpho-polycarboxylic acid radical unsubstituted.

Where the products are produced by reaction of amides of unsaturated aliphatic polycarboxylic acids followed by introduction of the sulphonic group by means of an alkali sulphite or bisulphite, the unsaturated polycarboxylic acids or derivatives thereofwhich may be utilized include, by way of example, maleic acid, fumaric acid, maleic acid anhydride, and the like. These and other derivatives may also be produced by initially preis otherwise .paring the aliphatic sulpho-polycarboxylic acid mono-cyclohexyl, beta-hydroxy-ethyl a min e i ethanol aniline; 1-amino-propanediol-2,3; monodecylolamine, mono-laurylol-amine, mono-hexadecylolamine, mono-octadecylolamine; monoand di-hydroxy polyamines derived, for example, from ethylene diamine, diethylene triamine, triethylene tetra-amine; monoand polyamines of sugars and sugar alcohols such as dextrose, sucrose, sorbitol, mannitol and dulcitol, and amines of polyhydric alcohols in general such as glycerol monoand di-amine; cyclic hydroxy amines including, for example, p-amino phenol,

and the like.

In the event that the sulphonic compounds of the present invention are made by reacting the halogen derivatives with an alkali sulphite or other soluble sulphites as well as thiosulphates, the corresponding alkali sulphonic acid derivative is produced. When prepared by other methods, other sulphonic acid salts may be produced or the alkali sulphonates can be converted into other salts by methods such as described in the application of Benjamin R. Harris, Serial No.

190,136, filed February 11, 1938, now Patent No.

2,166,144, issued July 18, 1939. Thus, the cation represented by M in the general formula set forth hereinabove may be calcium, magnesium, aluminum, zinc, organic nitrogenous bases as, for example, alcohol amines and alkylol-, aryloland aralkylol amines including mono, diand tri-ethanolamineand mixtures thereof such as are, for example, present in so-called commercial triethanolamine, propanolamines, b u t a n o l amines, pentanolamines, hexanolarnines, glycerolamines, glucamines, dibutyl ethanolamine, diethanol ethyl amine, cyclohexyl ethanolamine, diethanol cyciohexylamine, ethanol aniline, alkylol polyamines such as alkylol derivatives of ethylene diamine, mono-methyl m'onoethanolamine, diethyl-monoethanolamine, 1-amino-2,3

propanediol, 1, Z-diaminopropanol; alkylamines such as butyl amine, hexylamine, dimethylamine,

ethylene diamine, diethylene triamine, triethy lene tetra-amine, mono-methyl ethylene diamine, mono-ethyl diethylene tetra-amine, mono-allyl amine, aromatic and heterocyclic bases such as benzylamine, cyclo-hexylethyl-aniline, morpholine, pyridine, alkyl pyridines such as methylpyridine, piperidine, pyrrolidines, quinolines, quinaldine, nicotine, and homologues and derivatives or substitution products thereof; mix tures of any two or more thereof, and the like.

It will be understood that these organic bases,

as in the case of triethanolamine, for example, may be employed in pure, impure, or commercial form.

Instead of reacting the halogeno-poly-carboxylic acid amide of the alcohol primary or secondary amine, for example,

' with an alkali sulphite and an acyl halide, as

fying agents.

described hereinabove, the intermediate may be reacted with a salt of a higher molecular weight carboxylic acid or the like, such as sodium stearate, potassium laurate, sodium caprylate or Those skilled in the art will know, in the light of my teachings herein, the manner of preparing compounds of this type.

The compounds of this invention have utility in various arts in which interface modifying agents are employed. Many of them are resistant to precipitation by calcium and magnesium salts and are compatible with acid and alkali media. Various of them may be utilized in washing and laundering and in the textile and related industries wherein they function for softening, wetting, detergent, emulsifying, penetrating, dispersing, frothing, and foaming purposes.

The textiles, various treatments of which in thepresence of the agents of the present invention is rendered effective, comprise natural products such as cotton, wool, linen and the like as well as the artificially produced fibres, (and fabrics) such as rayon, cellulose acetates, cellulose ethers and similar artificial products. It will be understood, of course, that the agents may be used in aqueous and other media either alone or in'combination with other suitable salts of organicor inorganic character or with other interface modi- In the dyeing of textiles, many of them may be employed as assistants in order to They' may be used in the leather industry as wetting agents in soaking, dyeing, tanning and the softening and other treating baths for hides and skins. Their utility as emulsifying agents enables them to-be employed for the preparation of emulsions which in the preparation of cosmetic cream such as cold creams, vanishing creams, tissue creams, shavin creams of the brushless and lathering type and similar cosmetic preparations. Another use to which various of the agents of the present in-'- vention may be placed is for the treatment of paper pulp and paper where they may be employed, for example, as penetrating agents in the cooking of the paper pulp or the like. Their capillary or interfacial tension reducing properties enables them to be employed in the fruit and vegetable industry in order to effect the removal from fruits and the like of arsenical and similar sprays. They possess marked utility in the ore dressing industry wherein they function effectively in froth flotation processes. Their interface modifying properties also permit their use in lubricating oils and the like enabling the production of effective boring oils, cutting oils,

' sulphuric and sulphonic derivatives of condensadrilling oils, wire drawing oils, extreme pressure lubricants and the like. They may also be used with effect in the preparation of metal andfurniture polishes, shoe polishes, in rubber compositions', for breaking or demulsifying petroleum emulsions such'as those of the water-in-oil type which are encountered in oil-field operations, and for various other purposes which will readily occur to those versed in the art in the light of the disclosure herein.

As detergents, many of them may be employed for the preparation of shampoos, dentifrices and the like. In general, they may be dissolved in water or aqueous media and utilized inthat form or, in the case of solid products, they may be packaged and sold in such forni' preferably mixed with diluents. They may also be utilized for commercial cleansing, laundering and washing operations with marked advantage. I

The products of the present invention may be employed alone or together with lesser or greater quantities of inorganic or organic compounds. Thus, for example, they may be employed together with salts such as. sodium chloride, alkali metal phosphates, including pyrophosphates and tetraphosphates, sodium sulplate, alums, perborates such'as-sodium perborate, and the like. 'Ihey may be utilized in alkaline or acid media in the presence of sodium carbonate, sodium bicarbonate, dilute acids such as hydrochloric, sulphurous, acetic and similar inorganic and organic acids. They may also beemployed in the presence of such diverse substances as hydrophilic gums including pectin, tragacanth, karaya, locust bean, gelatin, ,arabic and the like, glue, vegetablaanimal, fish and mineral oils, solvents such as carbon tetrachloride, monoethyl ether of ethylene glycol, mpnobutyl ether of ethylene glycol, monoethyl and monobutyl ethers of diethylene glycol, cyclohexanol, and the like. They may. be used together with wetting, emulsifying, frothing, foaming, penetrating and detergent agents such as the higher molecular weight alkyl sulphates, phosphate, pyrophosphates and tetraphosphates as. for example, lauryl sodium sulphate, myristyl sodium pyrophosphate, cetyl sodium tetraphosphate, octyl sodium sulphate,

' oleyl sodium sulphate, and the like; higher molecular weight sulphonic acid derivatives such as cetyl sodium sulphonate'and iauryl sodium' sulphonate; sulphocarboxylic acid esters of higher arweight alcohols such as lauryl sodium molecul V sulphoacetate, dioctyl sodium sulphosuccinate,

tion products of alkylolamines and higher fatty acids; phosphoric, pyrophosphoric' and tetraphosphoric acid esters of higher molecular weight alcohols; Turkey-red oils; compounds of the type of isopropyl naphthalene sodium sulphonate and other classes of wetting agents.

It will be understoodthat, in all cases, there is present in the molecules of the sulphonic derivatives of the present invention at least one sul'-' phonic acid radical although, dependingupon the particular reacting ingredients and the proportions thereof utilized, more than one sulphonlc group may be introduced.

Wherever the term higher is employed as referring to higher molecular weight organicacids orthe like, it will be understood to cover compounds or radicalshaving at least eight carbon atoms unless otherwise specifically stated.

Whenever the term sulphonic group, sulphonic radical, sulphonic acid group, or the like expression is employed in the claims,-it will be under- 15, 1938, now Patent No. 2,184,770, issued.De-'

cember 26, 1939.

WhatI claim as new and desire to protect by Letters Patent of the United States is:

, products thereof, Y is a member selected from 1. Chemical compounds corresponding to the general formula wherein R. is a member selected from, the group consisting of acyl, alkyl and substituted alkyl radicals containing at least four carbon atoms,

alk is a member selected from the'group consisting of hydrocarbon radicals and substitution the group consisting of hydrogen, alkyl, cycloalkyl, alkoxyl, aralkyl, aryl, ant alkylol, -oo z is the carboxylic acyl radical of an aliphatic sulpho-polycarboxylic acid, and m is a whole number.

2. Chemical compounds corresponding to the general formula wherein RPc=o is an aliphatic acyl'radi'cal containing at least eightcarbon atoms, alk is a hydrocarbon radical, Y is a member selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkoxyl, aralkyl, aryl, andalkylol, and

than eight carbon atoms.

3. Chemical compoundscorresponding to the general formula. i

- boxylic acid.

' 5. Chemical compounds corresponding to the 20 wherein RC=O is an aliphatic acyl radical containing at least eight carbon atoms, all: is alkylene, Y is a member selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkoxyl,

aralkyl, aryl, and alkylol, and M and M cations.

4. Chemical compounds corresponding to the general formula RO (alk-NY) mCO-.-Z wherein R is a'member selected'from the group consisting of acyl', alkyl and substituted alkyl radicals containing at least four carbon atoms,

all: is hydrocarbon, Y is a member selected'from the group consisting of hydrogen, alkyl, cyclo alkyl, alkoxyl, aralkyl, aryl, and alkylol, m is a whole number, and COZ is the carboxylic acyl radical of an aliphatic sulpho-polycartaining from eight to eighteen carbon'atoma'and I M and M are cations.

8. Chemical compounds corresponding to the wherein RC=O is an aliphatic acyl radical containing at least eight carbon atoms, all: is

alkylene, and COZ is the carboxylic acyl radical of an aliphatic sulpho-dicarboxyiic acid containing not more than eight carbon atoms.

9. Chemical compounds corresponding to the formula CnHu('JOC:H4NH CO+CH:CH-CM wherein M and M.are alkali metals.

10. The process ofpreparing chemical com- 60.

pounds which comprises reacting an aliphatic poly-carboxylie acid amide of an alcohol amine with a member selected from the group consisting of carboxylic acids and halides thereof containing at least four carbon estertlinkage and with amember selected from the group consisting of sulphite and bisulphite salts tointroduce, a sulphonic 7 group into the molecule. W

11. The process of preparing chemical compounds which comprises reacting an aliphatic dicarboxylic acid-amide of a6 alkylol'amine. the dicarborylic acid radical having not more than eight carbon atoms, with an acyl halide containing from eight to eighteen carbon atoms, to form an ester linkage and with a member selected from the group consisting of sulphite and bisulphite are salts to introduce a sulphonic group into the molecule.

12. The process of preparing chemical compounds which comprises reacting maleic anvhydride with monoethanolamine to form an [0 amide thereof, and then reacting said amide, in

optional order, with a fatty acid acyl halide containing from eight to eighteencarbon atoms to form an ester linkage and with an alkali bisulphite to introduce a sulphonic group at the double bond of the maleic acid radical.

13. The process of preparingchemical compounds whichcomprises reacting an alkylol nontertiary amine with a member selected from the group consisting of unsaturated\ aliphatic dicarboxyliqacids and anhydrides thereof to form amides of said alkylol non-tertiary amine, and

then reacting said amides, in optional order, with a fatty acid acyl halide containing from eight to eighteen carbon atoms to formanester linkage and with an alkali bisulphite to introduce u a sulphonic group at a double bond of the dicarboxylic acid radical.

14. The process of preparing chemical compounds which comprises reacting an aliphatic halogeno-polycarboxylic acid amide of an alcohol aminewith a member selected from the group consisting of carboxylic acids and halides thereof containing at least four carbon atoms to'form.

an ester linkage and with a sulphite salt to reare placehalogen with a sulphonic group.

15. The process ofpreparin'g chemical com pounds which comprises reacting an alkylol nontertia amine with a mono-ethyl ester 01' a dicarboi'rylic acid selected from the groupcon'-- 0 sisting of maleic acid and fumaric acid, whereby an amide is formed, and then introducing, at opposite ends 0% the amide, a sulphonic group and a fatty acid radical containing from eight to eighteen carbon atoms.

16. The method of claim 15 wherein the alkylol non-tertiary amine comprises monoethanolamine.

17. The method of preparing chemical compounds which comprises reacting an ester of a member selected from the group consisting of phatic unsaturated polycarboxylic acids, having not more than eight carbon atoms, with an al-. cohol non-tertiary amine to form an amide, and

then introducing into the amide a sulphonic group and an organic radical selected from the group consisting of acyl, alkyl and substitutedalkyl radicals containing at least four carbon atoms.

pounds which comprises reacting a mono-ethyl ester oLamernber selected from the. group consisting oi maleic acid and fumaricacid, with vanalkylol non-tertiary amine to form an amide, and then introducing, into said amide a sulphonic atoms to form an group and a fatty acid-radical containing.irom eightto eighteen carbon atoms.

19. The method 01' claim 12 wherein the :sul-,

phonic group. is introduced into the molecule prior to trfiiintroduction of the fatty acid'radical.

The v non-tertiaryamine comprises diethanolamine.

' Moi-ems aliphatic halogeno-poly-carboxylic acids and ali-' is. The method of preparing chemical com-" ethod bi' claim-18 wherein'the 1 31x3101 

